CN105280940A - Method for coking wastewater degradation and synchronous power generation by taking coking active bacterium as biocatalyst - Google Patents

Method for coking wastewater degradation and synchronous power generation by taking coking active bacterium as biocatalyst Download PDF

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CN105280940A
CN105280940A CN201510591785.9A CN201510591785A CN105280940A CN 105280940 A CN105280940 A CN 105280940A CN 201510591785 A CN201510591785 A CN 201510591785A CN 105280940 A CN105280940 A CN 105280940A
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coking
carbon felt
bacterium
anode
phenol
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CN105280940B (en
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赵煜
樊磊
王俊文
李婷
梁镇海
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Taiyuan University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
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Abstract

The invention relates to a method for coking wastewater degradation and synchronous power generation by taking coking active bacterium as a biocatalyst. The method is carried out according to the following steps of partitioning a carbon-based active coking microbial film positive electrode and a platinum-loaded carbon fabric negative electrode at two chambers by using a cation membrane or a proton membrane; degrading organic matters and inorganic matters which are high in toxicity and are difficult to be degraded in coking wastewater in an anode anaerobic environment by using the coking active bacterium; allowing oxidation reaction; transferring electrons released through reaction to a positive carbon felt by a medium or a pigment secreted from the bacterium; sequentially transmitting the electrons to a negative electrode through an external wire; and allowing an electron acceptor of the negative electrode to generate reduction reaction. By the process, the treatment of high-toxicity and degradation-resistant coking wastewater is achieved, chemical energy reserved in the process is also converted to electrical energy, a new method is provided for coking wastewater treatment, and meanwhile, a wide prospect is provided for green treatment of the coking wastewater in future.

Description

Method using coke activity bacterium as biocatalyst treatment of Coking Wastewater synchronous electrogenesis
Technical field
The present invention relates to a kind of method of Treatment of Coking Effluent, especially a kind of using active coking bacterium as biocatalyst, wherein contained chemical energy is the method for electric energy by phenol, ammonia nitrogen, sulfide, these typical pollutants of cyanide in using microbe fuel cell technology treatment of Coking Wastewater simultaneously.
Background technology
The coke gross annual output amount of China is up to about 300,000,000 tons, occupies first place in the world in position.Meanwhile produced a large amount of coking chemical waste waters cause very big pollution to environment.Coking chemical waste water is by the organic wastewater of the high concentration produced in coking high-temperature retorting, quenching, gas purification and chemical products subtractive process, poisonous and harmful, complicated component.Wherein organic substance is based on phenols, and containing Multiple components such as phenol and homologue, cyanide, sulfide, especially ammonia nitrogen accounts for 50% ~ 70% of coking chemical waste water total amount.The discharge of coking chemical waste water can produce very strong toxic effect to aqueous bio, has stronger carcinogenesis simultaneously, causes very large threat to health.Therefore, find a kind of environmental protection and also efficiently coking waste water treatment method be realistic problem in the urgent need to address.
Existing coking waste water treatment method has Physical, chemical oxidization method, physico-chemical process, electrochemical process, biochemical process and multiple said method junction logos.Wherein biochemical processing method treatment effect is good, product toxic and side effect is little and be widely used.
Ye Zhengfang (China Environmental Science, 2002, macromolecule carrier 01:32-35) etc. is used to fix high-effective microorganism B350 (including 28 kinds of microbes and cellulase, amylase, hydrolase etc.), itself and aeration tank are formed organism fluidization bed system Treatment of Wastewater in Coking, COD clearance are 98.3%, volatile phenol clearance is 99.7%, NH 4+-N clearance is 99.9%.
Wang Jiaquan (environmental science, 2010,4:735-741) etc. utilize two room MFC microbiological fuel cell process phenolic waste water.Anode adopts stainless (steel) wire, and negative electrode is ti-supported lead dioxide electric, is cultivated by waste water treatment plant's anaerobic sludge in phenol and nutrient solution, puts into stainless (steel) wire so that growth of microorganism simultaneously, is transferred to by stainless (steel) wire afterwards in MFC battery and cultivates and electrogenesis.At initial phenol concentration 3.5gL -1time, clearance reaches 60%.
Ran Chunqiu (civil construction and environmental engineering, 2012, two room MFC 6:139-144) etc. is utilized to dispose of sewage, adopt anaerobic nitrification and denitrification mixing sludge, cultivate domestication anaerobic nitrification bacterium and denitrifying bacterium, utilize biological anodic oxidation to remove organic pollution, biological-cathode removes nitrogen-containing pollutant, two Room COD, NH 4 +-N and NO 3 -the highest clearance sum of N is respectively 67.0%, 76.9% and 84.0%.
Song Tianshun (regenerative resource, 2012,11:110-113) etc. start single chamber MFC with anaerobic sludge, and anaerobic sludge MFC peak power output when ammonia nitrogen concentration is 488.2mg/L is 454.6mW/m 2.
Mao Yanping (water technology, 2010,2:105-111) etc. utilizes microbiological fuel cell treatment of simulated sulfur-containing waste water, and sulfide can all be oxidized to elemental sulfur or sulfate.Water inlet carbon sulphur mass ratio is greater than 12.50:1, S 2-when mass concentration is 50mg/L, sulfide-oxidation becomes the conversion ratio of elemental sulfur to reach 61% ~ 77%.
Luo Haiping (ACTA Scientiae Circumstantiae, 2008,7:1279-1283) etc. utilize microbiological fuel cell, graphite granule is filled at negative and positive the two poles of the earth, bacterial classification is from municipal sewage plant, aerobic sludge and the mixing of anaerobic sludge equal-volume, the inoculation liquid being microbiological fuel cell with mud supernatant, adds 1000mgL simultaneously -1glucose is as the fuel of MFC.After the stable operation in several cycle, electrode forms stable biomembrane, with this degradation of phenol waste water.1000mgL -1when phenol is single-fuel operation, phenol clearance reaches about 90%.
Beam Zhenghai (Chemistry In China engineering journal, 2011,4:570-574) etc. utilize the method for electrochemical oxidation, with Ti/SnO2+Sb2O4/PbO2 electrode as work electrode, Pt is to electrode, saturated calomel electrode is reference electrode, under three-electrode system, do cyclic voltammetry experiment, and the ammonia nitrogen in research coking chemical waste water carries out the kinetics mechanism removed.
For above-mentioned existing coking waste water treatment method, still there is certain defect, be embodied in that treatment effeciency is low, cost is high, Partial digestion mode is too single, degraded is thorough, complex process, and energy consumption is high, can not chemical energy in effective recycling waste water.Biological fuel cell technical finesse coking chemical waste water relies on traditional biochemical processing method, tames, biochemical anaerobic bacteria and aerobic bacteria in this, as the biocatalyst of this technology under electrochemical environment.But without the need to power consumption, be electric energy by the chemical energy in waste water simultaneously, overcome the shortcoming that conventional biochemical method aeration energy consumption is high.
Summary of the invention
Based on the deficiency that above-mentioned prior art exists, the invention provides a kind of method using coke activity bacterium as biocatalyst treatment of Coking Wastewater synchronous electrogenesis.
A kind of method using coke activity bacterium as biocatalyst treatment of Coking Wastewater synchronous electrogenesis provided by the present invention, method described in it follows these steps to carry out:
(1) coking bacterium activation culture
The bacterium mud getting coke-oven plant's Aerobic Pond and anaerobic pond is 1:1 mixing by its mass ratio, is stored in refrigerating chamber for subsequent use.During use, be first placed in 4 DEG C of refrigerating chambers and thaw, get 200g bacterium mud afterwards and add 400ml coking bacteriotrophy liquid, activation culture 72-120 hour at 35 DEG C.
(2) anti-single toxicity matter dominated electrogenesis flora is cultivated in the domestication of co-substrate electrochemical gradient
First double-chamber microbiological fuel cell device is built.With carbon felt for anode, within 20% year, platinum carbon cloth, year nickel carbon felt and electrographite brush one are wherein negative electrode, respectively in coking chemical waste water four kinds of representative poisonous substance phenol, ammonium chloride, potassium sulfide, Cymag and glucose as co-substrate, using the good coking bacterium of activation culture as microbial catalyst, under permanent extrernal resistance pattern, electrochemistry cultivates anode electrogenesis microorganism species;
Add the good coking bacterium sludge solutions of 60ml activation culture in the anode compartment and 20ml glucose content is the anolyte of 1g/L, first respectively keep toxicant constant concentration: phenol 0.2g/L, ammonium chloride 0.075g/L, potassium sulfide 0.05/L, Cymag 0.008g/L, reduce concentration of glucose gradually to single phenol, ammonium chloride, potassium sulfide, Cymag toxicant; Reducing concentration of glucose is more successively: 1g/L, 0.5g/L, 0.25g/L and 0g/L; Finally gradient increases toxicant concentration respectively, is followed successively by: phenol 0.3g/L, 0.4g/L, 0.5g/L, 0.6g/L; Ammonium chloride 0.15g/L, 0.3g/L, 0.45g/L, 0.6g/L, 0.75g/L; Potassium sulfide 0.15g/L, 0.25g/L, 0.35g/L, 0.45g/L, 0.55g/L; Cymag 0.022g/L, 0.036g/L, 0.05g/L, 0.064g/L, 0.078g/L;
Take batch operational mode, continuous monitoring output voltage, when output voltage is reduced to 0.1V, change anolyte and catholyte simultaneously, repeat multiple cycle, until ceiling voltage that fuel cell exports tends towards stability, reach 0.5-0.6V, final anode carbon felt obtains domestication cultured phenol dominant bacteria, ammonia nitrogen dominant bacteria, sulfide dominant bacteria and cyanide dominant bacteria biomembrane.
(3) domestication for the treatment of of Coking Wastewater multiple pollutant microbial association is cultivated
The biomembrane of above-mentioned four Carbon felt surfaces is scraped, puts into coking bacteriotrophy liquid activation culture 72-120 hour in the lump together with the carbon felt shredded;
Add the good mixed coking bacterium sludge solutions of 60ml activation culture in the anode compartment and 20ml glucose content is the anolyte of 1g/L, control sludge concentration at 4000 ~ 4500mg/L;
Another interpolation four kinds of toxicant phenol 0.6g/L, ammonium chloride 0.75g/L, potassium sulfide 0.55/L, Cymag 0.078g/L, under permanent extrernal resistance pattern, electrochemistry is cultivated;
Take batch operational mode, continuous monitoring output voltage, when output voltage is reduced to 0.1V, change anolyte and catholyte simultaneously, repeat multiple cycle, until ceiling voltage that fuel cell exports tends towards stability, final anode carbon felt obtains the associating coking electrogenesis bacterium biomembrane of the cultured phenol of simultaneously degrading of domestication, ammonia nitrogen, sulfide, cyanide.
(4) treatment of Coking Wastewater synchronous electrogenesis
Using associating coking electrogenesis bacterium carbon felt good for above-mentioned domestication as anode, anode chamber squeezes into coking chemical waste water continuously by feed pump, and cathode chamber squeezes into catholyte continuously by feed pump, and negative and positive room is separated by amberplex.Access low-power electrical device in the closed circuit, periodic monitor battery two ends output voltage, monitors delivery port water quality situation simultaneously, and determines the need of returning stream accordingly, achieve Treatment of Wastewater in Coking and simultaneously electrogenesis, its peak power output density reaches 630mW/m 2.
In the above-described embodiment, the composition of described coking bacteriotrophy liquid and content thereof are: glucose 1g/L, NH 4cl0.31g/L, KCl0.13mg/L, NaH 2pO 42H 2o6.64g/L, Na 2hPO 412H 2o20.64g/L, CaCl 20.01g/L; MgSO 41.2g/L; NaCl0.002g/L; FeSO 46mg/L; MnSO 40.76mg/L; AlCl 30.5mg/L; (NH 4) 6mo 7o 243mg/L; H 3bO 31mg/L; NiCl 26H 2o0.1mg/L; CuCl 20.53816mg/L; ZnCl 21mg/L; CoCl 22H 2o1mg/L;
Described anode is three groups of carbon felt materials, first carries out chemical treatment:
(1) red fuming nitric acid (RFNA) and 5% hydrogenperoxide steam generator that volume ratio is 5:1 is configured;
(2) by carbon felt as in solution, ultrasonic cleaning 30min;
(3) the ultrasonic carbon felt processed is placed in crucible, under 450 DEG C of conditions, heats 3h;
(4) take out carbon felt distilled water repeatedly to rinse, until pH is 7, vacuumize 15h 150 DEG C time.
Again graphene oxide electro-deposition is carried out to chemical-treated carbon felt:
(1) with the sodium hydrogen phosphate of 49ml0.1mol/L and the sodium dihydrogen phosphate of 51ml0.1mol/L, configuration pH is the phosphate buffer solution of 6.8;
(2) by graphene oxide ultrasonic dissolution 8h in phosphate buffer solution, the graphene solution of 5mg/ml is mixed with;
(3) cyclic voltammetry deposited graphite alkene: use carbon felt to make work electrode, platinum guaze is done electrode, and Ag/AgCl electrode makes reference electrode.Potential scan scope is set: 0-1.6v, sweeps speed: 5mV/s, scan 70 circles altogether.
Described negative electrode is 20% year platinum carbon cloth, carries nickel carbon felt and electrographite brush one wherein.
Composition and the content thereof of described anolyte are: glucose 1g/L, NH 4cl0.31g/L, KCl0.13mg/L, NaH 2pO 42H 2o6.64g/L, Na 2hPO 412H 2o20.64g/L and 20mlWolfe microelement nutritious liquid, its pH is 7.
Composition and the content thereof of described catholyte are: K 3[Fe (CN) 6], Na 2hPO 412H 2o and NaH 2pO 42H 2o is 3:1:6 preparation according to mass ratio, regulates its pH to be 7.
Composition and the content thereof of described coking chemical waste water toxicant are: sulfide 141.6mg/L, volatile phenol 225.9mg/L, ammonia nitrogen 210mg/L, cyanide 15.7mg/L and COD1800mg/L.
Described domesticated strain and coking chemical waste water fuel-cell device comprise: anode chamber and cathode chamber, use cationic membrane to be separated two Room.Two carbon felt anodes are closely pressed against in stainless (steel) wire support both sides, form a carbon felt-stainless (steel) wire-carbon felt sandwich structure unit, and sandwich structure unit stainless steel wire is connected and staggered, forms full of twists and turns coking chemical waste water passage therebetween.Negative electrode stainless steel wire is connected equidistant arrangement.Coking chemical waste water successively through oil removal treatment process and removal suspended matter, pumps into from one end, anode chamber, by the biological transmembrane channels of carbon felt anode, flows out, or carry out circulating reflux again from the other end; Catholyte pumps into from one end, flows out from the other end.
What realize that the invention described above provides is a kind of to tame ripe coking bacterium as catalyst, utilize the method for microbiological fuel cell technique to high-efficiency treatment of Coking Wastewater synchronous electrogenesis, to realize while treatment of Coking Wastewater middle and high concentration high toxic material, recycle the chemical energy of toxicant, reach waste water treatment and electrogenesis integration.
This method greatly reduces the cost of waste water treatment, simplify coking waste water treatment process, without the need to the operating process of complexity, achieve the high degradation rate of toxicant, green, clean, environmental protection, turn waste into wealth, reach the effect of high-efficiency sewage process and the effective and reasonable preparation of resource, have both environment and ecological benefits, Social benefit and economic benefit.Also for waste water treatment, tapping a new source of energy provides an effective approach, for the development of new forms of energy from now on provides more wide prospect.
Existing coking waste water treatment method operating procedure is complicated, cost is high, treatment effeciency is low, degraded is thorough, can not chemical energy in effective recycling waste water.Compared with prior art, advantage of the present invention and good effect embody a concentrated reflection of following several aspect:
The co-substrate electrochemical gradient domestication training method that this method adopts, can strengthen the antitoxin adaptability of bacterium gradually, is conducive to filtering out efficient, that stable, mithridatism is strong electrogenesis flora.
This method utilizes fixed bed pattern, compares with conventional biochemical method, and occupied space is little, treatment facility simple, flexible operation, can adopt continuous tupe or batch (-type) tupe according to effluent quality.
This method operating procedure is simple, does not need to be equipped with the aerator in conventional biochemical method, Non-energy-consumption, and effective, the clean no coupling product of Treatment of Coking Effluent, can not bring environmental pollution.
This method waste water treatment consuming cost is low, it is low to invest, and can be electric energy by the chemical energy in useless Organic substance in water and inorganic matter, have certain economic benefit, for new energy development from now on provides new approaches.
Accompanying drawing explanation
Fig. 1 is principle of microbial fuel cells structural representation of the present invention.
Fig. 2 is domesticated strain device of the present invention and coking chemical waste water fuel-cell device structural representation.
Fig. 3 is output voltage variation relation in time in phenol in the present invention, ammonia nitrogen, sulfide, cyanide dominant bacteria domestication process.
Output voltage variation relation in time in Fig. 4 associating coking electrogenesis bacterium domestication process.
Coking chemical waste water fuel cell output power density and current density change relation when Fig. 5 is battery stable operation of the present invention.
Fig. 6 is Battery disposal coking chemical waste water 5 days front and back infrared absorption spectroscopy comparison diagrams of stable operation of the present invention.
Fig. 7 is battery stable operation of the present invention trimestral carbon felt electrode surface scan Electronic Speculum figure.
Fig. 8 is battery stable operation of the present invention three months associating coking electrogenesis bacterium 16sRNA door horizontal proportion figure.
Fig. 9 is battery stable operation of the present invention three months associating coking electrogenesis bacterium 16sRNA guiding principle horizontal proportion figure.
Figure 10 is that battery stable operation of the present invention three months associating coking electrogenesis bacterium 16sRNA belong to horizontal proportion figure.
Embodiment
Below concrete technical scheme of the present invention is described in further detail.
1, this is a kind of to tame ripe coke activity bacterium as biocatalyst, utilizes poisonous in microbiological fuel cell technology treatment of Coking Wastewater and the method for the pollutant of difficult degradation.Use two rooms system, anolyte is coking chemical waste water, and catholyte is potassium ferricyanide solution.
2, anode totally three groups of carbon felt materials, totally three groups, described negative electrode, is 20% year platinum carbon cloth, carries nickel carbon felt and electrographite brush one wherein.
3, on MFC anolyte (pH=7) basic composition basis, concentration of glucose is reduced gradually according to concentration gradient 1g/L, 0.5g/L, 0.25g/L and 0g/L, gradient increases phenol, ammonium chloride, potassium sulfide, sodium cyanide concentration simultaneously, be extremely finally pure toxicant, then increase each toxicant concentration gradually.Adopt batch operational mode.
4, phenol dominant bacteria, ammonia nitrogen dominant bacteria, sulfide dominant bacteria, cyanide dominant bacteria admixture activation are cultivated, inoculate in anode chamber, add four kinds of toxicant phenol 0.6g/L, ammonium chloride 0.75g/L, potassium sulfide 0.55/L, Cymag 0.078g/L in anolyte basic composition, the associating electrogenesis bacterium for the treatment of of Coking Wastewater multiple pollutant is cultivated in last electrochemistry domestication.Adopt batch operational mode.
5, cultured associating electrogenesis bacterium Treatment of Wastewater in Coking is adopted.Coking chemical waste water major toxicity material: sulfide 141.6mg/L, volatile phenol 225.9mg/L, ammonia nitrogen 210mg/L, cyanide 15.7mg/L and COD1800mg/L.
Below by specific embodiment, the specific embodiment of the present invention is further detailed.
Embodiment 1
Utilize a method for microbiological fuel cell treatment of Coking Wastewater synchronous electrogenesis using coke activity bacterium as biocatalyst, method described in it is carried out by the following step.
1, MFC phenol and the domestication of glucose co-substrate system electrochemistry: activated sludge takes from certain disposal of coking plant waste water workshop Aerobic Pond and anaerobic pond, build double-chamber microbiological fuel cell device, phenol and glucose co-substrate system is adopted in anode chamber, cathode chamber is potassium ferricyanide solution, negative electrode is 20% year platinum carbon cloth, keep 35 DEG C of constant temperatures, the permanent extrernal resistance of external 1000 Ω, Timing measurement external voltage.Battery adopts intermittent operation mode, when output voltage is less than 0.1V, changes anolyte and catholyte.Originally arranging phenol concentration is 0.2g/L, and concentration of glucose is 1g/L, two cycles of continuous service; Keep the amount of phenol constant, reduce concentration of glucose gradually, the concentration of getting glucose is respectively 1g/L, 0.5g/L, 0.25g/L and 0g/L; Then continuously increase single phenol substrate concentration for four times and be respectively 0.3g/L, 0.4g/L, 0.5g/L, 0.6g/L; Last repetition under 0.6g/L phenol concentration is tamed to output voltage stabilization, indicates that biomembrane is ripe.Finally inoculate and culture out the advantage electrogenesis flora of degradation of phenol.In MFC start-up course, electrogenesis function bacterium on carbon felt anode is constantly run with battery and is adapted to electrochemical environment and matrix environment gradually, the phenol dominant bacteria adapting to anaerobism electric field environment is better than other population and obtains flourish, adsorb gradually at anode surface, enrichment and then domestication are formed has the biomembrane of electro-chemical activity, so the start-up course of battery is biomembranous forming process in fact, be also screening and the enrichment process of anode drop phenol dominant bacteria simultaneously.
2, the ammonium chloride of MFC is identical with described in 1 with glucose co-substrate system domestication step, just matrix used and concentration difference thereof.Originally ammonium chloride concentration is 0.075g/L, and concentration of glucose is 1g/L, two cycles of continuous service; Keep the amount of ammonium chloride constant, reduce the consumption of glucose gradually, the concentration of getting glucose is respectively 1g/L, 0.5g/L, 0.25g/L and 0g/L, then continuously increase single ammonium chloride substrate concentration for five times and be respectively 0.15g/L, 0.3g/L, 0.45g/L, 0.6g/L, 0.75g/L; Last repetition under 0.75g/L ammonium chloride concentration is tamed to output voltage stabilization.Finally inoculate and culture out the advantage electrogenesis bacterium of degradation of ammonia nitrogen.
3, the potassium sulfide of MFC is identical with described in 1 with glucose co-substrate system domestication step, just matrix used and concentration difference thereof.Originally potassium sulfide is 0.05/L, and glucose is 1g/L, and the concentration of glucose alternation is 1g/L, 0.5g/L, 0.25g/L and 0g/L; Then continuously increase single potassium sulfide substrate concentration for five times and be respectively 0.15g/L, 0.25g/L, 0.35g/L, 0.45g/L, 0.55g/L; Last repetition under 0.55g/L potassium sulfide concentration is tamed to output voltage stabilization.Finally inoculate and culture out the advantage electrogenesis bacterium of degraded sulfide.
4, the Cymag of MFC is identical with described in 1 with glucose co-substrate system domestication step, just matrix used and concentration difference thereof.Originally sodium cyanide concentration is 0.008g/L, and concentration of glucose is 1g/L, and the concentration of glucose alternation is 1g/L, 0.5g/L, 0.25g/L and 0g/L; Then continuously increase single Cymag substrate concentration for five times and be respectively 0.022g/L, 0.036g/L, 0.05g/L, 0.064g/L, 0.078g/L; Last repetition under 0.078g/L sodium cyanide concentration is tamed to output voltage stabilization.Finally inoculate and culture out the advantage electrogenesis bacterium of degraded cyanide.
5, glucose is utilized--toxicant co-substrate system inoculates and cultures out four kinds of typical pollutant dominant bacterias in coking chemical waste water respectively: phenol dominant bacteria, ammonia nitrogen dominant bacteria, sulfide dominant bacteria, cyanide dominant bacteria; Mixed again, first activation culture in coking bacteriotrophy liquid, in the anolyte containing phenol 0.6g/L, ammonium chloride 0.75g/L, potassium sulfide 0.55g/L, Cymag 0.078g/L, electrochemistry domestication is cultivated again, finally obtains the associating coking electrogenesis bacterium of phenol of simultaneously degrading, ammonia nitrogen, sulfide, cyanide.
6, the actual coking chemical waste water of associating coking electrogenesis bacterium continuous degradation is utilized, and timing sampling, detect each component index of waste water.
7, coking chemical waste water porch: COD1800mg/L, sulfide 141.6mg/L, volatile phenol 225.9mg/L, ammonia nitrogen 210mg/L, cyanide 15.7mg/L in the above-described embodiment, after degraded in 5 days, exit: COD105.6mg/L, sulfide 0.64mg/L, phenol 0.17mg/L, ammonia nitrogen 3.4mg/L, cyanide 1.5mg/L, peak power output density 630mW/m 2.COD clearance 94.1%, phenol clearance 99.9%, ammonia nitrogen removal frank 98.4%, sulfide clearance 99.5%, cyanide clearance 90.4%, coulombic efficiency 70%.
Coulombic efficiency measures
Coulombic efficiency is: E = Σ i = 1 n U i t i R F b Δ c V M - - - ( 1 )
In formula (1), U i, t imoment output voltage; R, external resistance; F, Faraday constant, 96485C/mol; The electron number that b, 1molCOD are corresponding, 4e -mol/mol; Δ c, COD remove concentration; V, matrix volume; M, oxygen molecule amount, 32g/mol.
Embodiment 2
Present embodiment adopts as different from Example 1 and carries nickel carbon felt is negative electrode, and other steps are identical with embodiment 1.In the present embodiment, coulombic efficiency is 62.1%, and coking chemical waste water COD clearance is 63.5%, and peak power output density is 509mW/m 2.
Embodiment 3
Present embodiment adopts electrographite brush to be negative electrode as different from Example 1, and other steps are identical with embodiment 1.In the present embodiment, coulombic efficiency is 49.6%, and coking chemical waste water COD clearance is 52.6%, maximum output 611mW/m 2.
Accompanying drawing 3 be in phenol dominant bacteria, ammonia nitrogen dominant bacteria, sulfide dominant bacteria, cyanide dominant bacteria domestication process output voltage with domestication the time graph of a relation.Represent that when output voltage is constant biomembrane is ripe, strain domestication completes, and wherein the phenol dominant bacteria domestication time is 705h, and the ammonia nitrogen dominant bacteria domestication time is 796h, and the sulfide dominant bacteria domestication time is 807h, and the cyanide dominant bacteria domestication time is 729h.
Output voltage variation relation in time in accompanying drawing 4 associating coking electrogenesis bacterium domestication process.Represent that when output voltage is constant biomembrane is ripe, strain domestication completes.The coking electrogenesis bacterium domestication time is 620h.
Accompanying drawing 5 is coking chemical waste water fuel cell output power density, output voltage and output current density relationship figure, and maximum power output density is 630mW/m 2.
Accompanying drawing 6 is Treatment of Coking Effluent 5 days front and back infrared absorption spectroscopy comparison diagrams.Comparing with before process, there is significantly change in the characteristic absorption peak of some functional group.Wherein 3455cm before process -1place and the rear 3449cm of process -1in the wideband that place occurs, intensity absorption band is caused, comprising the hydroxyl in organic substance and the hydrogen bond association in organic substance by the association state stretching vibration of hydrogen bond.After process, 1721cm -1place, 1635cm -1place's absworption peak is the stretching vibration of C=O; 825cm -1place, 862cm -1place is the flexural vibrations of C-H on phenyl ring; 1124cm -1place, 1074cm -1place is the stretching vibration of C-O-C in two kinds of ethers.Before process, 1383cm -1locate to vibrate for the in-plane deformation of phenol.After process, 1383cm -1place, 1434cm -1place is-CH 2-CH 3absworption peak.Coking chemical waste water MFC is in the process of electrogenesis, and some materials are degraded, and generates again new intermediate product simultaneously.
Accompanying drawing 7 runs trimestral carbon felt electrode surface scan electron microscopic picture for inoculating coking chemical waste water, and on anode carbon felt, electrogenesis mixed bacterial bacterial density is very large, has bacillus, coccus and flocculence thing, wherein based on coccus, has thread line to be connected between bacterium.
Accompanying drawing 8,9,10 is respectively active coking bacterium 16sRNA, uses 16sRNA door, guiding principle, genus horizontal proportion figure.In door level, wherein Proteobacteria accounts for 56.23%, Firmicutes account for 21.02% and Bacteroidetes account for 10.98%; Microbial population is divided into 21 guiding principles, and wherein clostridium accounts for 20.82%, and distortion Gammaproteobacteria accounts for 54.63%, and also have methagen guiding principle, abnormal club Gammaproteobacteria etc. occupies ratio and is less than 0.1%.In genus level, ground Bacillus accounts for 10.32%, and Thermomonospora accounts for 8.96% in addition, anaerobism acetobacter accounts for 4.23%, and fixed nitrogen vibrio accounts for 4.02%.
Table 1
Upper table 1 is the 7 days front and back coking chemical waste water turnover water quality index of process continuously.

Claims (8)

1. the method using coke activity bacterium as biocatalyst treatment of Coking Wastewater synchronous electrogenesis, described method follows these steps to carry out:
(1) coking bacterium activation culture
The bacterium mud getting coke-oven plant's Aerobic Pond and anaerobic pond is 1:1 mixing by its mass ratio, is stored in refrigerating chamber for subsequent use; During use, be first placed in 4 DEG C of refrigerating chambers and thaw, get 200g bacterium mud afterwards and add 400ml coking bacteriotrophy liquid, activation culture 72-120 hour at 35 DEG C;
(2) anti-single toxicity matter dominated electrogenesis flora is cultivated in the domestication of co-substrate electrochemical gradient
First double-chamber microbiological fuel cell device is built for domesticated strain and Treatment of Wastewater in Coking, with carbon felt for anode, within 20% year, platinum carbon cloth, year nickel carbon felt and electrographite brush one are wherein negative electrode, respectively in coking chemical waste water four kinds of representative poisonous substance phenol, ammonium chloride, potassium sulfide, Cymag and glucose as co-substrate, using the good coking bacterium of activation culture as microbial catalyst, under permanent extrernal resistance pattern, electrochemistry cultivates anode electrogenesis microorganism species;
Add the good coking bacterium sludge solutions of 60ml activation culture in the anode compartment and 20ml glucose content is the anolyte of 1g/L, first respectively toxicant constant concentration is kept, phenol 0.2g/L, ammonium chloride 0.075g/L, potassium sulfide 0.05g/L, Cymag 0.008g/L, reduce concentration of glucose gradually to single phenol, ammonium chloride, potassium sulfide, Cymag toxicant; Reducing concentration of glucose is more successively: 1g/L, 0.5g/L, 0.25g/L and 0g/L; Finally gradient increases toxicant concentration respectively, is followed successively by: phenol 0.3g/L, 0.4g/L, 0.5g/L, 0.6g/L; Ammonium chloride 0.15g/L, 0.3g/L, 0.45g/L, 0.6g/L, 0.75g/L; Potassium sulfide 0.15g/L, 0.25g/L, 0.35g/L, 0.45g/L, 0.55g/L; Cymag 0.022g/L, 0.036g/L, 0.05g/L, 0.064g/L, 0.078g/L;
Take batch operational mode, continuous monitoring output voltage, when output voltage is reduced to 0.1V, change anolyte and catholyte simultaneously, repeat multiple cycle, until ceiling voltage that fuel cell exports tends towards stability, reach 0.5-0.6V, final anode carbon felt obtains domestication cultured phenol dominant bacteria, ammonia nitrogen dominant bacteria, sulfide dominant bacteria and cyanide dominant bacteria biomembrane;
(3) domestication for the treatment of of Coking Wastewater multiple pollutant microbial association is cultivated
The biomembrane of above-mentioned four Carbon felt surfaces is scraped, puts into coking bacteriotrophy liquid activation culture 72-120 hour in the lump together with the carbon felt shredded;
Add the good mixed coking bacterium sludge solutions of 60ml activation culture in the anode compartment and 20ml glucose content is the anolyte of 1g/L, control sludge concentration at 4000 ~ 4500mg/L;
Another interpolation four kinds of toxicant phenol 0.6g/L, ammonium chloride 0.75g/L, vulcanized sodium 0.55g/L, Cymag 0.078g/L, under permanent extrernal resistance pattern, electrochemistry is cultivated;
Take batch operational mode, continuous monitoring output voltage, when output voltage is reduced to 0.1V, change anolyte and catholyte simultaneously, repeat multiple cycle, until ceiling voltage that fuel cell exports tends towards stability, final anode carbon felt obtains the associating coking electrogenesis bacterium biomembrane of the cultured phenol of simultaneously degrading of domestication, ammonia nitrogen, sulfide, cyanide;
(4) treatment of Coking Wastewater synchronous electrogenesis
Using associating coking electrogenesis bacterium carbon felt good for above-mentioned domestication as anode, anode chamber squeezes into coking chemical waste water continuously by feed pump, cathode chamber squeezes into catholyte continuously by feed pump, negative and positive room is separated by amberplex, accesses low-power electrical device in the closed circuit, determines the need of returning stream according to water quality situation, monitor battery two ends output voltage simultaneously, periodic monitor delivery port water quality situation, realize Treatment of Wastewater in Coking and simultaneously electrogenesis, its peak power output density reaches 630mW/m 2.
2. method according to claim 1, composition and the content thereof of described coking bacteriotrophy liquid are: glucose 1g/L, NH 4cl0.31g/L, KCl0.13mg/L, NaH 2pO 42H 2o6.64g/L, Na 2hPO 412H 2o20.64g/L, CaCl 20.01g/L; MgSO 41.2g/L; NaCl0.002g/L; FeSO 46mg/L; MnSO 40.76mg/L; AlCl 30.5mg/L; (NH 4) 6mo 7o 243mg/L; H 3bO 31mg/L; NiCl 26H 2o0.1mg/L; CuCl 20.53816mg/L; ZnCl 21mg/L; CoCl 22H 2o1mg/L.
3. method according to claim 1, described anode is three groups of carbon felt materials, first carries out chemical treatment:
(1) red fuming nitric acid (RFNA) and 5% hydrogenperoxide steam generator that volume ratio is 5:1 is configured;
(2) carbon felt is placed in solution, ultrasonic cleaning 30min;
(3) the ultrasonic carbon felt processed is placed in crucible, at 450 DEG C, heats 3h with Muffle furnace;
(4) take out carbon felt distilled water repeatedly to rinse, until pH is 7,150 DEG C of vacuumize 15h;
Further graphene oxide electro-deposition is carried out to chemical-treated carbon felt again:
(1) mixed by the sodium dihydrogen phosphate of the sodium hydrogen phosphate of 49ml0.1mol/L and 51ml0.1mol/L, configuration pH is the phosphate buffer solution of 6.8;
(2) by graphene oxide ultrasonic dissolution 8h in phosphate buffer solution, the graphene solution of 5mg/ml is mixed with;
(3) cyclic voltammetry deposited graphite alkene: use carbon felt to make work electrode, platinum guaze is done electrode, and Ag/AgCl electrode makes reference electrode.Potential scan scope is set: 0-1.6v, sweeps speed: 5mV/s, scan 70 circles altogether.
4. method according to claim 1, described negative electrode is 20% year platinum carbon cloth, carries nickel carbon felt and electrographite brush one wherein.
5. method according to claim 1, composition and the content thereof of described anolyte are: glucose 1g/L, NH 4cl0.31g/L, KCl0.13mg/L, NaH 2pO 42H 2o6.64g/L, Na 2hPO 412H 2o20.64g/L and 20mlWolfe microelement nutritious liquid, its pH is 7.
6. method according to claim 1, composition and the content thereof of described catholyte are: by K 3[Fe (CN) 6], Na 2hPO 412H 2o and NaH 2pO 42H 2o is 3:1:6 preparation according to mass ratio, regulates its pH to be 7.
7. method according to claim 1, composition and the content thereof of described coking chemical waste water toxicant are: sulfide 141.6mg/L, volatile phenol 225.9mg/L, ammonia nitrogen 210mg/L, cyanide 15.7mg/L and COD1800mg/L.
8. method according to claim 1, described double-chamber microbiological fuel cell device, comprises anode chamber and cathode chamber, and uses cationic membrane to be separated two Room; Two carbon felt anodes are closely pressed against in stainless (steel) wire support both sides, form a carbon felt-stainless (steel) wire-carbon felt sandwich structure unit, and sandwich structure unit stainless steel wire is connected and staggered, forms full of twists and turns coking chemical waste water passage therebetween; Negative electrode stainless steel wire is connected equidistant arrangement; Coking chemical waste water successively through oil removal treatment process and removal suspended matter, pumps into from one end, anode chamber, by the biological transmembrane channels of carbon felt anode, flows out from the other end; Or carry out circulating reflux again; Catholyte pumps into from one end, flows out from the other end.
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CN107349781A (en) * 2017-06-27 2017-11-17 浙江大学 A kind of efficient removal ultrahigh concentration NOxMicroorganism orientation acclimation method
CN107349781B (en) * 2017-06-27 2019-11-08 浙江大学 A kind of efficient removal ultrahigh concentration NOxMicroorganism orientation acclimation method
CN107140752A (en) * 2017-06-30 2017-09-08 太原理工大学 A kind of Treatment of Wastewater in Coking synchronously produces the device and method of hydrogen
CN107377608A (en) * 2017-07-18 2017-11-24 常州大学 It is a kind of efficiently to remove Cr in acid soil6+Microbial fuel cell unit and method
CN107881825A (en) * 2017-11-17 2018-04-06 苏州博进生物技术有限公司 The microbial treatment method of scrap based on fireworks firecracker firing generation rubbish
CN107881825B (en) * 2017-11-17 2019-10-18 苏州博进生物技术有限公司 The microbial treatment method of scrap based on fireworks firecracker firing generation rubbish
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